JP4582815B2 - Internal standard substance, mass spectrometric method using the same, and internal standard resin - Google Patents
Internal standard substance, mass spectrometric method using the same, and internal standard resin Download PDFInfo
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- JP4582815B2 JP4582815B2 JP2008115331A JP2008115331A JP4582815B2 JP 4582815 B2 JP4582815 B2 JP 4582815B2 JP 2008115331 A JP2008115331 A JP 2008115331A JP 2008115331 A JP2008115331 A JP 2008115331A JP 4582815 B2 JP4582815 B2 JP 4582815B2
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- 239000000126 substance Substances 0.000 title claims description 75
- 239000011347 resin Substances 0.000 title claims description 29
- 229920005989 resin Polymers 0.000 title claims description 29
- 238000004949 mass spectrometry Methods 0.000 title claims description 26
- 239000000523 sample Substances 0.000 claims description 27
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 17
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 claims description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 5
- 239000010422 internal standard material Substances 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical group OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 description 25
- 229910021645 metal ion Inorganic materials 0.000 description 14
- -1 phenol compound Chemical class 0.000 description 11
- 230000008021 deposition Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 230000008016 vaporization Effects 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 6
- 238000005192 partition Methods 0.000 description 6
- KUGBQWBWWNPMIT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentan-1-ol Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(O)(F)F KUGBQWBWWNPMIT-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005421 electrostatic potential Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/0009—Calibration of the apparatus
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/24—Nuclear magnetic resonance, electron spin resonance or other spin effects or mass spectrometry
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
Description
本発明は、質量分析を用いて樹脂に含まれる臭素化難燃剤の定量に用いられる内部標準物質とそれを用いた質量分析方法、及び内部標準樹脂に関する。 The present invention relates to an internal standard substance used for quantification of a brominated flame retardant contained in a resin using mass spectrometry, a mass spectrometry method using the same, and an internal standard resin.
近年、ヨーロッパ連合 EUが定めたRoHS（Restriction of Hazardous Substances）規制により、 EU域内へ輸出を行う場合、製品に使用されている樹脂に含まれる臭素化難燃剤が、規定値以上含有されていないことを証明する必要が生じている。 In recent years, according to RoHS (Restriction of Hazardous Substances) regulations established by the European Union EU, brominated flame retardants contained in resins used in products must not contain more than the specified value. Need to prove.
そのため、規制の対象物質である臭素化難燃剤を正確に定量することへの社会的な要求が高まってきている。 Therefore, there is an increasing social demand for accurately quantifying brominated flame retardants that are subject to regulation.
このような社会背景の中、検体を加熱して気化する質量分析において、内部標準物質を被測定物質に添加して測定し、その内部標準物質との比較で定量的な測定を行う質量分析が行われてきた。非特許文献１には、ＩＡＭＳ(Ion Attachment Mas Spectrometry)を用いてRoHS難燃剤の定量分析を行うことが開示されている。
上述の状況のもと、臭素化難燃剤のような被測定物質に対して加熱して気化させて質量分析を行う場合、検体に添加する内部標準物質が熱分解することなく、毒性もなく、さらに被測定物質と内部標準物質との質量数が近いことなどの条件を満たすことが求められる。しかし、これらの条件を満たし、かつ、被測定物質を正確に定量できる内部標準物質は今まで確認されていなかった。 Under the above-mentioned circumstances, when performing mass spectrometry by heating and vaporizing a substance to be measured such as a brominated flame retardant, the internal standard substance added to the sample is not thermally decomposed and has no toxicity. Furthermore, it is required to satisfy the conditions such as the mass number of the substance to be measured and the internal standard substance being close. However, an internal standard substance that satisfies these conditions and can accurately quantify the substance to be measured has not been confirmed so far.
ここで検体とは、質量分析装置の測定にかけられる状態に準備された被測定物質等からなる物質をいう。 Here, the specimen refers to a substance made of a substance to be measured and the like prepared in a state to be subjected to measurement by a mass spectrometer.
本発明の目的は上記の問題を鑑み、質量分析を用いて樹脂中の臭素化難燃剤を定量する際に使用する内部標準物質、内部標準樹脂、及びそれを用いる質量分析方法を提供することにある。 In view of the above problems, an object of the present invention is to provide an internal standard substance, an internal standard resin, and a mass spectrometry method using the same, which are used when quantifying a brominated flame retardant in a resin using mass spectrometry. is there.
本発明者は上記の条件を満足する内部標準物質を鋭意検討した結果、内部標準物質として好適に用いることのできる物質及びそれを用いた測定方法を見いだし、本発明に想到した。 As a result of intensive investigation of internal standard substances that satisfy the above conditions, the present inventor has found a substance that can be suitably used as an internal standard substance and a measurement method using the substance, and have arrived at the present invention.
本発明にかかる内部標準物質、内部標準樹脂、及び質量分析方法は、次のとおりである。 The internal standard substance, internal standard resin, and mass spectrometry method according to the present invention are as follows.
本発明に係わる内部標準物質は、ヒンダートフェノール化合物を有することを特徴とする、検体を加熱して気化する質量分析に用いる内部標準物質であり、さらに好ましくは1,6-ヘキサンジオールビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕(CAS#: 35074-77-2)を有する内部標準物質である。 The internal standard substance according to the present invention is an internal standard substance used for mass spectrometry for heating and vaporizing a specimen, characterized by having a hindered phenol compound, and more preferably 1,6-hexanediol bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate] (CAS #: 35074-77-2).
本発明に係わる内部標準樹脂は、検体を加熱して気化する質量分析に用いられる内部標準物質が母材である樹脂に含有されて構成される、前記検体に添加される内部標準樹脂であって、前記内部標準物質がヒンダートフェノール化合物を有することを特徴とする内部標準樹脂であり、さらに好ましくは1,6-ヘキサンジオールビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕（CAS#：35074-77-2）である内部標準樹脂である。 The internal standard resin according to the present invention is an internal standard resin added to the specimen, wherein the internal standard substance used for mass spectrometry for heating and vaporizing the specimen is contained in a resin as a base material. An internal standard resin characterized in that the internal standard substance has a hindered phenol compound, and more preferably 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionate] (CAS #: 35074-77-2).
本発明に係わる質量分析方法は、検体を加熱して気化する質量分析法であって、検体に添加する内部標準物質としてヒンダートフェノール化合物を使用し、さらに好ましくは1,6-ヘキサンジオールビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕(CAS#: 35074-77-2)を使用することを特徴とする質量分析方法である。 The mass spectrometric method according to the present invention is a mass spectrometric method for heating and vaporizing a specimen, using a hindered phenol compound as an internal standard substance added to the specimen, more preferably 1,6-hexanediol bis [ 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (CAS #: 35074-77-2) is used.
ここで、ヒンダートフェノール化合物とは、フェノール化合物の水酸基に対し、そのオルト位置に分岐アルキル基を持つ化合物をいう。但し、水酸基がアルコキシ基であってもよい。 Here, the hindered phenol compound refers to a compound having a branched alkyl group at the ortho position with respect to the hydroxyl group of the phenol compound. However, the hydroxyl group may be an alkoxy group.
また、1,6-ヘキサンジオールビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕(CAS#: 35074-77-2)の化学式はC40H62O6で表され、構造式を以下に示す。 The chemical formula of 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (CAS #: 35074-77-2) is C 40 H 62 O 6 . The structural formula is shown below.
質量数は６３８である。 The mass number is 638.
本発明によれば、検体に添加される内部標準物質として、熱分解することなく、毒性もなく、さらに被測定物質と内部標準物質との質量数が近いヒンダートフェノール化合物を用い、質量分析をすることで正確な定量測定をすることができる。 According to the present invention, as an internal standard substance added to a specimen, a hindered phenol compound that is not thermally decomposed, has no toxicity, and has a mass number close to that of the substance to be measured and the internal standard substance is used for mass spectrometry. By doing so, accurate quantitative measurement can be performed.
以下、本発明の実施の形態について図面を用いて詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
本実施形態で説明される構成・形状・大きさおよび位置関係については本発明が理解・実施できる程度に概略化したものに過ぎない。 従って本発明は以下に説明される実施形態に限定されるものではなく、 特許請求の範囲に示される技術的思想の範囲を逸脱しない限り様々な形態に変更することができる。 The configuration, shape, size, and positional relationship described in the present embodiment are merely schematic to the extent that the present invention can be understood and implemented. Therefore, the present invention is not limited to the embodiments described below, and various modifications can be made without departing from the scope of the technical idea shown in the claims.
検体を加熱して気化し、ガス状となった被測定物質を測定する質量分析装置の一例として、直接導入プローブ(DIP) を用いて金属イオンをガス化した被測定物質に付着させる質量分析装置の例を図１に示した。 As an example of a mass spectrometer that heats and vaporizes a sample and measures a gas-to-be-measured substance, a mass spectrometer that attaches metal ions to the gasified substance to be measured using a direct introduction probe (DIP) An example of this is shown in FIG.
図１のように、質量分析装置として例えば、フラグメントを生成させることのないイオン付着質量分析装置を使用して、本発明の実施形態に係る質量分析法を説明する。尚、他のフラグメントを生成させることのないイオン化法として、Ｈ3Ｏ+からのＨ+転移によるＰＴＲ（Proton Transfer Reaction）、及び水銀イオンなどからの電荷交換によるＩＭＳ(Ion Molecule Spectrometer)なども利用することができる。 As shown in FIG. 1, the mass spectrometry method according to the embodiment of the present invention will be described using, for example, an ion attachment mass spectrometer that does not generate fragments as a mass spectrometer. As ionization methods that do not generate other fragments, PTR (Proton Transfer Reaction) by H + transfer from H 3 O + and IMS (Ion Molecule Spectrometer) by charge exchange from mercury ions, etc. are also used. can do.
まず、イオン付着質量分析装置の構成を説明する。
図１において、１１はイオン付着室、１３は中間室、１４は質量分析室である。イオン付着室１１には金属イオン放出体（エミッタ）１７が配置され、付着領域１２でイオン付着が行われる。イオン付着室１１は専用の真空排気ポンプ１６で真空状態にされ、エミッタ１７と付着領域１２は同じ真空環境下に置かれる。
First, the configuration of the ion attachment mass spectrometer will be described.
In FIG. 1, 11 is an ion attachment chamber, 13 is an intermediate chamber, and 14 is a mass spectrometry chamber. A metal ion emitter (emitter) 17 is disposed in the ion deposition chamber 11, and ion deposition is performed in the deposition region 12. The ion deposition chamber 11 is evacuated by a dedicated evacuation pump 16 and the emitter 17 and the deposition region 12 are placed in the same vacuum environment.
金属イオン放出体１７は、例えば正電荷のリチウムイオン（Ｌｉ＋）を付着領域１２に放出する。また付着領域１２に対しては、プローブ１のヒータ３により、検体４を加熱気化させて検体４のガスが供給される。プローブ１は、イオン付着室１１とゲートバルブ９を介して接続されている予備排気室１０より導入される。プローブ１には、検体４の温度を測定する熱電対２も備えられている。 The metal ion emitter 17 emits, for example, positively charged lithium ions (Li + ) to the adhesion region 12. Further, the sample 4 is heated and vaporized by the heater 3 of the probe 1 and the gas of the sample 4 is supplied to the adhesion region 12. The probe 1 is introduced from a preliminary exhaust chamber 10 connected to the ion attachment chamber 11 via a gate valve 9. The probe 1 is also provided with a thermocouple 2 that measures the temperature of the specimen 4.
その結果、加熱気化した検体４のガスは矢印１８のように付着領域１２に向かって上昇し、矢印１９のように放出され金属イオンが検体４のガスに付着して、付着イオンが生成される。 As a result, the gas of the sample 4 that has been vaporized by heating rises toward the adhesion region 12 as indicated by an arrow 18 and is released as indicated by an arrow 19 so that the metal ions adhere to the gas of the sample 4 and generate adhering ions. .
図１において、矢印２０は金属イオンと付着イオンの移動の軌跡を示している。なお、プローブ１の導入位置は、イオン付着室１１内で同じ真空環境下が維持されていればよく、図１に示す位置に限定されない。 In FIG. 1, an arrow 20 indicates the locus of movement of metal ions and attached ions. The introduction position of the probe 1 is not limited to the position shown in FIG. 1 as long as the same vacuum environment is maintained in the ion attachment chamber 11.
イオン付着室１１と中間室１３との間には、孔２１ａを有した隔壁２１が設けられている。隔壁２１の孔２１ａを通して金属イオンと付着イオンが移動する。中間室１３には、図示しない定電圧機構によって静電位が印加されているレンズ２２が与えられている。このレンズ２２によって静電レンズ作用が生じる。 A partition wall 21 having a hole 21 a is provided between the ion adhesion chamber 11 and the intermediate chamber 13. Metal ions and attached ions move through the holes 21 a of the partition walls 21. The intermediate chamber 13 is provided with a lens 22 to which an electrostatic potential is applied by a constant voltage mechanism (not shown). This lens 22 causes an electrostatic lens action.
中間室１３と質量分析室１４の間には、孔２４ａを有した隔壁２４が設けられている。隔壁２４の孔２４ａを通して付着イオンが質量分析室１４に輸送される。質量分析室１４の内部には、例えばＱポール型（四重極型）等の質量分析計２５が設けられ、かつ共用の真空排気ポンプ２６が付設されている。質量分析計２５の図中右側には付着イオンを受ける二次電子増倍管２７が配置されている。 A partition wall 24 having a hole 24 a is provided between the intermediate chamber 13 and the mass spectrometry chamber 14. The attached ions are transported to the mass spectrometry chamber 14 through the holes 24a of the partition wall 24. A mass spectrometer 25 such as a Q pole type (quadrupole type), for example, is provided inside the mass analysis chamber 14, and a common vacuum pump 26 is attached. On the right side of the mass spectrometer 25 in the figure, a secondary electron multiplier 27 for receiving attached ions is arranged.
イオン付着室１１、中間室１３、質量分析室１４は、真空排気ポンプ１６、２６による真空排気で、大気圧以下の減圧雰囲気となっている。イオン付着室１１でアルカリ金属の酸化物である金属イオン放出体１７は加熱され、Ｌｉ＋などの正電荷の金属イオンを発生する。 金属イオン放出体１７は、図示しない電源によって所要の電圧が印加されて電流が供給され、加熱される。この加熱によって金属イオン放出体１７から金属イオンが放出される。放出された金属イオンは電界等によってイオン付着室１１内部の付着領域１２に輸送される。 The ion adhesion chamber 11, the intermediate chamber 13, and the mass analysis chamber 14 are evacuated by the evacuation pumps 16 and 26, and have a reduced-pressure atmosphere below atmospheric pressure. The metal ion emitter 17, which is an alkali metal oxide, is heated in the ion deposition chamber 11 to generate positively charged metal ions such as Li + . The metal ion emitter 17 is heated by being supplied with a required voltage by a power source (not shown) and supplied with a current. By this heating, metal ions are released from the metal ion emitter 17. The released metal ions are transported to the adhesion region 12 inside the ion adhesion chamber 11 by an electric field or the like.
検体４に添加される内部標準物質は、1,6-ヘキサンジオールビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕(CAS#: 35074-77-2)が用いられる。ここで、検体が樹脂の場合、測定精度を高めるため内部標準物質を母材と呼ばれる樹脂に混ぜ込んで内部標準樹脂とすることが望ましい。つまり、内部標準物質は、樹脂である被測定物質と同様に、母材と呼ばれるその熱伝導性が被測定物質と近い樹脂に混ぜ込まれて内部標準樹脂とされることが望ましい。さらに、このとき内部標準物質を粉末にすることで母材への分散は良好になる。 The internal standard substance added to specimen 4 is 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (CAS #: 35074-77-2). Used. Here, when the specimen is a resin, it is desirable to mix the internal standard substance with a resin called a base material to improve the measurement accuracy. That is, it is desirable that the internal standard material is mixed with a resin whose thermal conductivity called a base material is close to that of the material to be measured to be the internal standard resin, similarly to the material to be measured which is a resin. Further, at this time, by dispersing the internal standard substance into a powder, the dispersion into the base material becomes good.
また、母材に対する本発明に係る内部標準物質の含有率は、重量比で０．１〜５％であることが好ましい。０．1％未満であると感度が十分でなくなり、５％を超えると感度が高過ぎるからである。母材としては、例えば、ポリスチレンを用いることができる。 Moreover, it is preferable that the content rate of the internal standard substance which concerns on this invention with respect to a base material is 0.1 to 5% by weight ratio. This is because the sensitivity is insufficient when it is less than 0.1%, and the sensitivity is too high when it exceeds 5%. As the base material, for example, polystyrene can be used.
なお、検体に対する内部標準樹脂の質量比は、１０〜７５％であることが望ましい。１０％未満では秤量が困難になるからであり、７５％を超えると感度が高過ぎるからである。 The mass ratio of the internal standard resin to the specimen is desirably 10 to 75%. This is because weighing is difficult if it is less than 10%, and sensitivity is too high if it exceeds 75%.
さらに、検体を質量分析装置に導入して加熱して気化する方法は、図1のように直接導入プローブ法（ＤＩＰ）を用いたが、直接曝露プローブ法（ＤＥＰ）を用いることもできる。 Furthermore, although the direct introduction probe method (DIP) is used as the method of introducing the sample into the mass spectrometer and heating and vaporizing it as shown in FIG. 1, the direct exposure probe method (DEP) can also be used.
直接導入プローブ法は、固体または液体の被測定物質をカップの中に入れて真空のイオン付着室内に導入し、その場でヒータや赤外線などで加熱して気化させる方法であり、
一方、 直接曝露プローブ法は、固体または液体の被測定物質をフィラメントに塗布し真空のイオン付着室内に挿入し、その場でフィラメントに通電して被測定物質を加熱して気化させる方法である。
The direct introduction probe method is a method in which a solid or liquid substance to be measured is introduced into a cup and introduced into a vacuum ion deposition chamber, and is heated and vaporized by a heater or infrared rays on the spot.
On the other hand, the direct exposure probe method is a method in which a solid or liquid substance to be measured is applied to a filament, inserted into a vacuum ion deposition chamber, and the substance to be measured is heated and vaporized by energizing the filament on the spot.
また、本実施形態に係わる内部標準物質を添加して定量分析可能な検体中の被測定物質は、樹脂に含まれる臭素化難燃剤を挙げることができる。臭素化難燃剤としては、例えば、デカブロモジフェニルエーテル (DeBDE, CAS#:1163-19-5) 、デカブロモビフェニル (DeBB, CAS#: 13654-09-6) を挙げることができる。 Examples of the substance to be measured in the specimen that can be quantitatively analyzed by adding the internal standard substance according to the present embodiment include brominated flame retardants contained in the resin. Examples of brominated flame retardants include decabromodiphenyl ether (DeBDE, CAS #: 1163-19-5) and decabromobiphenyl (DeBB, CAS #: 13654-09-6).
なお、内部標準物質は、既に説明したように、検体を加熱して気化させる場合、それに添加する内部標準物質が熱分解しないこと、毒性がないこと、内部標準物質と被測定物質との質量数が近いこと等が求められる。 As already explained, when the sample is heated and vaporized, the internal standard is not thermally decomposed, non-toxic, and the mass number of the internal standard and the substance to be measured. Is required.
内部標準物質としては、ヒンダートフェノール化合物が用いられる。ヒンダートフェノール化合物は、フェノール化合物の水酸基に対し、そのオルト位置に分岐アルキル基を持つ化合物をいう。但し、水酸基がアルコキシ基であってもよい。ヒンダートフェノール化合物の中でも、1,6-ヘキサンジオールビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕(CAS#: 35074-77-2)が好適に用いられる。 As the internal standard substance, a hindered phenol compound is used. The hindered phenol compound refers to a compound having a branched alkyl group at the ortho position with respect to the hydroxyl group of the phenol compound. However, the hydroxyl group may be an alkoxy group. Among the hindered phenol compounds, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (CAS #: 35074-77-2) is preferably used. .
内部標準物質としての1,6-ヘキサンジオールビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕(CAS#: 35074-77-2)は、後述の測定方法に説明があるとおり、気化に必要な３００℃で分解することがなく、市販されている化学物質として毒性のないことが確認されている。また、臭素化難燃剤のデカブロモジフェニルエーテル (DeBDE, CAS#:1163-19-5) 、デカブロモビフェニル (DeBB, CAS#: 13654-09-6) の質量数は、それぞれ
９５９Ｄａ、９４３Ｄａであり内部標準物質の質量数との関係も適している。
1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (CAS #: 35074-77-2) as an internal standard is As explained, it does not decompose at 300 ° C. required for vaporization, and it is confirmed that it is not toxic as a commercially available chemical substance. The mass numbers of brominated flame retardants decabromodiphenyl ether (DeBDE, CAS #: 1163-19-5) and decabromobiphenyl (DeBB, CAS #: 13654-09-6) are 959 Da and 943 Da, respectively. The relationship with the mass number of the standard substance is also suitable.
従って、気化温度が内部標準物質と近く、内部標準物質と被測定物質との質量数が近い等の上記の条件を満たせば、他の検体材料の内部標準物質として、本実施形態の内部標準物質を用いることができる。 Therefore, if the above conditions such as the vaporization temperature is close to the internal standard substance and the mass number of the internal standard substance and the substance to be measured are close, the internal standard substance of this embodiment is used as the internal standard substance of other specimen materials. Can be used.
次に、図１に図示した質量分析装置を用いて、本実施形態に係る内部標準物質で例えば被測定物質としてデカブロモジフェニルエーテル (DeBDE, CAS#:1163-19-5)を定量分析する質量分析方法を説明する。 Next, using the mass spectrometer shown in FIG. 1, the mass spectrometry for quantitatively analyzing, for example, decabromodiphenyl ether (DeBDE, CAS #: 1163-19-5) as the substance to be measured with the internal standard substance according to this embodiment. A method will be described.
内部標準物質である1,6-ヘキサンジオールビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕(CAS#: 35074-77-2)を母材であるポリスチレンに1%含む内部標準樹脂を0.21ｍｇ秤量した。続いて被測定物質であるデカブロモジフェニルエーテル (DeBDE, CAS#: 1163-19-5) が含有されている検体を1.10ｍｇ秤量した。 1,6-Hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (CAS #: 35074-77-2), an internal standard substance, was added to the base polystyrene. 0.21 mg of internal standard resin containing 1% was weighed. Subsequently, 1.10 mg of a sample containing decabromodiphenyl ether (DeBDE, CAS #: 1163-19-5) as a substance to be measured was weighed.
内部標準樹脂と被測定物質をともに検体４としてプローブ１に充填し、イオン付着室１１を所定の真空度にしてプローブ1をイオン付着室１１に導入した。このとき、中間室１３及び質量分析室１４の真空度等、測定が可能な状態にある。 Both the internal standard resin and the substance to be measured were filled in the probe 1 as the specimen 4, and the probe 1 was introduced into the ion adhesion chamber 11 with the ion adhesion chamber 11 set to a predetermined degree of vacuum. At this time, the degree of vacuum of the intermediate chamber 13 and the mass spectrometry chamber 14 can be measured.
次に金属イオン放出体１７を加熱した状態で、検体４を設定した時間に従って300℃まで加熱し気化させた。 Next, with the metal ion emitter 17 heated, the specimen 4 was heated to 300 ° C. and vaporized according to the set time.
この構成で得られたデータを図２に示す。 The data obtained with this configuration is shown in FIG.
最上段のグラフは、常に一定導入されているオクタフルオロペンタノール (OFPO) の検出量である。通常、測定中の感度変動を確認するためこのような内部標準物質による補正が行われるが後述のように充分ではないことが明らかになっている。 The top graph shows the detected amount of octafluoropentanol (OFPO), which is always introduced constantly. Normally, correction by such an internal standard is performed to confirm the sensitivity fluctuation during measurement, but it has been revealed that this is not sufficient as described later.
図２の中段は、内部標準物質1,6-ヘキサンジオールビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕(CAS#: 35074-77-2)の検出値、下段は被測定物質であるデカブロモジフェニルエーテル (DeBDE, CAS#:1163-19-5) の検出値である。 The middle part of Fig. 2 shows the detected value of the internal standard substance 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (CAS #: 35074-77-2). The lower row shows the detection value of decabromodiphenyl ether (DeBDE, CAS #: 1163-19-5), which is the substance to be measured.
このように、1,6-ヘキサンジオールビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕(CAS#: 35074-77-2)の面積値は、92833294であり、デカブロモジフェニルエーテル (DeBDE, CAS#: 1163-19-5) の面積値は5777349であった。 Thus, the area value of 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (CAS #: 35074-77-2) is 92833294. The area value of decabromodiphenyl ether (DeBDE, CAS #: 1163-19-5) was 5777349.
この比率をあらかじめ作成した検量線にあてはめた結果、被測定物質であるデカブロモジフェニルエーテル(DeBDE, CAS#: 1163-19-5)は0.67μgであり、被分析対象である被測定物質（DeBDE）を含んだ樹脂中の濃度は610ppmと定量された。 As a result of applying this ratio to a calibration curve prepared in advance, the decabromodiphenyl ether (DeBDE, CAS #: 1163-19-5) to be measured is 0.67 μg, and the analyte to be analyzed (DeBDE) The concentration in the resin containing was determined to be 610 ppm.
次に三条件の場合、即ち、内部標準物質として1,6-ヘキサンジオールビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕(CAS#: 35074-77-2)を使った場合、OFPOを用いた場合、及び、内部標準物質を全く用いない場合とに分けて、上記と同じ測定を5回繰り返して行い、その繰り返し精度（相対標準偏差）を確認した。 Next, in the case of three conditions, that is, as an internal standard substance, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (CAS #: 35074-77-2 ), When using OFPO, and when using no internal standard at all, the same measurement as above was repeated 5 times, and the repeatability (relative standard deviation) was confirmed.
その結果、内部標準物質として1,6-ヘキサンジオールビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕(CAS#: 35074-77-2)を使った場合の相対標準偏差は4.3%であり、OFPOを用いた場合は13.4%、そして、内部標準物質を全く用いない場合は10.8%であり、測定精度が向上して大きな改善効果が認められた。 As a result, when 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (CAS #: 35074-77-2) was used as the internal standard substance. The relative standard deviation was 4.3%, 13.4% when OFPO was used, and 10.8% when no internal standard was used. The measurement accuracy was improved and a large improvement effect was recognized.
同じ臭素化難燃剤であるデカブロモビフェニル (DeBB, CAS#: 13654-09-6)についても同様な改善効果が認められた。 The same improvement effect was observed for decabromobiphenyl (DeBB, CAS #: 13654-09-6), the same brominated flame retardant.
本発明は、臭素化難燃剤及び同様な気化温度、質量数を有する被測定物質の定量分析に用いることができる。 The present invention can be used for quantitative analysis of a brominated flame retardant and a substance to be measured having the same vaporization temperature and mass number.
１ プローブ
２ 熱電対
３ ヒータ
４ 検体
９ ゲートバルブ
１０ 予備排気室
１１ イオン付着室
１２ 付着領域
１３ 中間室
１４ 質量分析室
１６ 真空排気ポンプ
１７ 金属イオン放出体（エミッタ）
２１ 隔壁
２１ａ 孔
２２ レンズ
２４ 隔壁
２４ａ 孔
２５ 質量分析計
２６ 真空排気ポンプ
DESCRIPTION OF SYMBOLS 1 Probe 2 Thermocouple 3 Heater 4 Specimen 9 Gate valve 10 Preliminary exhaust chamber 11 Ion attachment chamber 12 Adhesion region 13 Intermediate chamber 14 Mass analysis chamber 16 Vacuum exhaust pump 17 Metal ion emitter (emitter)
21 partition wall 21a hole 22 lens 24 partition wall 24a hole 25 mass spectrometer 26 vacuum pump
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